Process for preparing formyl diamines



Patented June 23, 1942 I I UNITED STATES PATENT OFFICE 2 PROCESS FOR PREPARING FORMYL DIAMINES Alva L. Houk, Philadelphia, Pa.., assignor to Riihm & Haas Company, Philadelphia, Pa.

No Drawing. Application November 8, 1940, Serial No. 364,843

Claims. (01. 260-584) This invention relates to compounds of the Example 2 formula A mixture of 70 parts of methacrolein, 120

(I353 parts of tetramethyl methylene diamine, and 9 NCHzC-CH;-N 5 parts of Water was stirred on a steam bath for R2 CH0 R: one and one-half hours and left standing overnight. The reaction mixture was then subjected Wherem R1 a1 1d R2 are ahphatlc hydrocarbon to distillation under reduced pressure and a fracgroups. This invention also concerns a process t of 12 parts collected which boiled between for preparing these compounds, wherein methaand 4 at 32 mm The i l t croleifl is reacted- With a N,NN"N"a1iphatica11y weight of this rather wide cut, 88.5, indicates substituted methylene diamine. t t it i the same product as was Obtained in The N,N,N',N'-aliphatical1y substituted meth- Example ylene diamine may be prepared by the reaction Eggample 3 of aliphatic secondary amines with formaldehyde or a polymer thereof. As an aliphatic secondary amine there may be used dimethylamine, diethylamine, diisobutylamine, diallylamine, methylcaprylamine, methyldodecylamine, or the like. The resulting ditertiary methylene dia- A mixture of 120 parts of tetraethyl methylene diamine, 52.5 parts of methacrolein, and 6.75 parts of water was stirred for one and one-half hours on a water bath at 90 C. After the reacted mixture had stood for three hours, the

water layer which had separated was removed and the organic layer distilled under reduced pressure. There Was obtained 77 parts of a liquid boiling at 147 C. at 26 mm. This liquid has mine has the structure NCHzN an equivalent weight of 117 and corresponds to A diamine of this formula and methacrolein I are mixed and heated at reacting temperatures, oiH5 r-NoHicoHiN(oiHt)i preferably in the presence of a small amount of E water as a catalyst. The temperature of reaction may be between about C. and about 150 C. The reaction is most conveniently carried out by heating the reacting mixture" on a water bath or, if an organic solvent be used, by heating under reflux. The reaction may also be carried out under pressure. The following examples illustrate the preparation of the formyl diamines.

Compounds of the above type are useful in the 39 textile field, reacting with cellulose under heat to modify the surface thereof. They are also useful intermediates for the preparation of quaternary ammonium derivatives, which are particularly useful as textile assistants and for the modification of cellulosic fibers, yarns, and fabrics. By the reaction of cellulosic materials with the formyl diamines of this invention the swell- Example 1 ing properties and also the dyeing properties A mixture of 70 parts of methacrolein, 105 thereof are altered. The treated cellulosic maparts of t t t methylen diamine and 6 49 terial may thus be rendered resistant to Water. parts of Water was stirred for five hours on a I 01mm: Water bath held at C. The reaction mixture T process of p p g N,N,N'-,N'-al1- was then subjected to distillation under reduced Phatlcany Substituted formyl diamines which pressure and 113 parts of a product boiling F comprises reacting by heating between about tween 90 and C, at 28 mm. was collected. and about in the presence of This product is a colorless liquid which is inso1u small amount of Water methacrolein and a comble in Water but Somme in dilute acids. It slow- Pound of the frmu1a ly reduces ammoniacal silver nitrate. After re- R1 R1 distillation at 90-96 c. at 22 mm. the product K l .10 has an equivalent Weight of 87.8, corresponding fairly closely with that for CH3 wherein R1 and R2 are aliphatic hydrocarbon CH N C 1 'groups. 3)7- Hi-( J-oH,-N 0Hi)i 2. The process of preparing N,N,N,N-ali- CHO 55 phatically substituted formyl diamines which comprises heating between about 70 C. and about 150 C. a mixture containing methacrolein, a small amount of water, and a compound of the formula R1\ /R1 N-CHr-N R3 R1 wherein R1 and R2 are aliphatic hydrocarbon wherein R1 and R2 are aliphatic hydrocarbon groups.

4. The process of preparin N,N,N',N-tetramethyl substituted formyl diamines which comprises heating between about 70" C. and about 150 C. a mixture of methacrolein, a small amount of water, and N,N,N',N'-tetramethyl methylene diamine.

5. The process of preparing N,N,N',N'-tetraethyl substituted formyl diamines which comprises heating between about 70 C. and about 150 C. a mixture of methacrolein, a small amount of water, and N,N,N,N'-tetraethy1 methylene diamine.

ALVA L. HOUK. 

